Neutral and Charged 1-Butyl-3-methylimidazolium Triflate Clusters: Equilibrium Concentration in the Vapor Phase and Thermal Properties of Nanometric Droplets

Ground state energy, structure, and harmonic vibrational modes of 1-butyl-3-methylimidazolium triflate ([bmim][Tf]) clusters have been computed using an all-atom empirical potential model. Neutral and charged species have been considered up to a size (30 [bmim][Tf] pairs) well into the nanometric range. Free energy computations and thermodynamic modeling have been used to predict the equilibrium composition of the vapor phase as a function of temperature and density. The results point to a nonnegligible concentration of very small charged species at pressures (P ~ 0.01 Pa) and temperatures (T 600 K) at the boundary of the stability range of [bmim][Tf]. Thermal properties of nanometric neutral droplets have been investigated in the 0 T 700 K range. A near-continuous transition between a liquidlike phase at high T and a solidlike phase at low T takes place at T ~ 190 K in close correspondence with the bulk glass point Tg ~ 200 K. Solidification is accompanied by a transition in the dielectric properties of the droplet, giving rise to a small permanent dipole embedded into the solid cluster. The simulation results highlight the molecular precursors of several macroscopic properties and phenomena and point to the close competition of Coulomb and dispersion forces as their common origin.

Space and phase resolved plasma parameters in an industrial dual-frequency capacitively coupled radio-frequency discharge

The dynamics of high energetic electrons (>= 11.7 eV) in a modified industrial confined dual-frequency capacitively coupled RF discharge (Exelan, Lam Research Inc.), operated at 1.937 MHz and 27.118 MHz, is investigated by means of phase resolved optical emission spectroscopy. Operating in a He-O-2. plasma with small rare gas admixtures the emission is measured, with one-dimensional spatial resolution along the discharge axis. Both the low and high frequency RF cycle are resolved. The diagnostic is based on time dependent measurements of the population densities of specifically chosen excited rare gas states. A time dependent model, based on rate equations, describes the dynamics of the population densities of these levels. Based on this model and the comparison of the excitation of various rare gas states, with different excitation thresholds, time and space resolved electron temperature, propagation velocity and qualitative electron density as well as electron energy distribution functions are determined. This information leads to a better understanding of the dual-frequency sheath dynamics and shows, that separate control of ion energy and electron density is limited.

Iron abundances of B-type post-asymptotic giant branch stars in globular clusters: Barnard29 in M13 and ROA5701 in ωCen

High-resolution optical and ultraviolet (UV) spectra of two B-type post-asymptotic giant branch (post-AGB) stars in globular clusters, Barnard29 in M13 and ROA5701 in ?Cen, have been analysed using model atmosphere techniques. The optical spectra have been obtained with FEROS on the ESO 2.2-m telescope and the 2d-Coudé spectrograph on the 2.7-m McDonald telescope, while the UV observations are from the Goddard high-resolution spectrograph on the Hubble Space Telescope (HST). Abundances of light elements (C, N, O, Mg, Al and S) plus Fe have been determined from the optical spectra, while the UV data provide additional Fe abundance estimates from FeIII absorption lines in the 1875-1900 Å wavelength region. A general metal underabundance relative to young B-type stars is found for both Barnard29 and ROA5701. These results are consistent with the metallicities of the respective clusters, as well as with previous studies of the objects. The derived abundance patterns suggest that the stars have not undergone a gas-dust separation, contrary to previous suggestions, although they may have evolved from the AGB before the onset of the third dredge-up. However, the Fe abundances derived from the HST spectra are lower than those expected from the metallicities of the respective clusters, by 0.5 dex for Barnard29 and 0.8 dex for ROA5701. A similar systematic underabundance is also found for other B-type stars in environments of known metallicity, such as the Magellanic Clouds. These results indicate that the FeIII UV lines may yield abundance values which are systematically too low by typically 0.6 dex and hence such estimates should be treated with caution.

Clusters, liquids and crystals of dialkylimidazolium salts. A combined perspective from ab initio computer simulations

We summarize results obtained by a combination of ab initio and classical computer simulations of dialkylimidazolium ionic liquids in different states of aggregation, from crystals to liquids and clusters. Unusual features arising from the competition between electrostatic, dispersion, and hydrogen-bonding interactions are identified at the origin of observed structural patterns. We also discuss the way Brønsted acids interact with ionic liquids leading to the formation of hydrogen-bonded anions.

Neural modelling, control and optimisation of an industrial grinding process

This paper describes the development of neural model-based control strategies for the optimisation of an industrial aluminium substrate disk grinding process. The grindstone removal rate varies considerably over a stone life and is a highly nonlinear function of process variables. Using historical grindstone performance data, a NARX-based neural network model is developed. This model is then used to implement a direct inverse controller and an internal model controller based on the process settings and previous removal rates. Preliminary plant investigations show that thickness defects can be reduced by 50% or more, compared to other schemes employed. (c) 2004 Elsevier Ltd. All rights reserved.

Model calculations for copper clusters on Au(111) surfaces

Using the semi-empirical embedded-atom method, the structure of small copper clusters on Au(111) surfaces has been investigated both by static and dynamic calculations. By varying the size of roughly circular clusters, the edge energy per atom is obtained; it agrees quite well with estimates based on experimental results. Small three-dimensional clusters tend to have the shape of a pyramid, whose sides are oriented in the directions of small surface energy. The presence of a cluster is found to distort the underlying lattice of adsorbed copper atoms. (C) 2002 Published by Elsevier Science B.V.